CN105308088B - Polyalcohol, preparation method and use containing tannin - Google Patents
Polyalcohol, preparation method and use containing tannin Download PDFInfo
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- CN105308088B CN105308088B CN201480034672.2A CN201480034672A CN105308088B CN 105308088 B CN105308088 B CN 105308088B CN 201480034672 A CN201480034672 A CN 201480034672A CN 105308088 B CN105308088 B CN 105308088B
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- polyalcohol
- tannin
- containing tannin
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- 150000005846 sugar alcohols Polymers 0.000 title claims abstract description 89
- 229920001864 tannin Polymers 0.000 title claims abstract description 76
- 235000018553 tannin Nutrition 0.000 title claims abstract description 76
- 239000001648 tannin Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 72
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 48
- 239000000203 mixture Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 45
- 239000003054 catalyst Substances 0.000 claims description 27
- 235000011187 glycerol Nutrition 0.000 claims description 24
- 150000002460 imidazoles Chemical class 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 23
- 235000016462 Mimosa pudica Nutrition 0.000 claims description 15
- 230000001186 cumulative effect Effects 0.000 claims description 15
- 235000011517 Terminalia chebula Nutrition 0.000 claims description 13
- 235000015489 Emblica officinalis Nutrition 0.000 claims description 12
- 239000004814 polyurethane Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 8
- -1 Oxygen alkane Chemical class 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 239000001294 propane Substances 0.000 claims description 4
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 244000277583 Terminalia catappa Species 0.000 claims 2
- 229910052760 oxygen Inorganic materials 0.000 claims 2
- 239000001301 oxygen Substances 0.000 claims 2
- 240000001140 Mimosa pudica Species 0.000 claims 1
- 241000220324 Pyrus Species 0.000 claims 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims 1
- 150000003851 azoles Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229920001461 hydrolysable tannin Polymers 0.000 claims 1
- 235000021017 pears Nutrition 0.000 claims 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 28
- 239000012467 final product Substances 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 239000000376 reactant Substances 0.000 description 19
- 238000003756 stirring Methods 0.000 description 19
- 241001070944 Mimosa Species 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 14
- 241000001522 Terminalia chebula Species 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 238000007789 sealing Methods 0.000 description 5
- 229930006000 Sucrose Natural products 0.000 description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 4
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- 239000005720 sucrose Substances 0.000 description 4
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000005445 natural material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241000220479 Acacia Species 0.000 description 1
- 241000993444 Acacia mearnsii Species 0.000 description 1
- 235000011468 Albizia julibrissin Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- 229920005897 Lupranol® 3300 Polymers 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/487—Polyethers containing cyclic groups
- C08G18/4879—Polyethers containing cyclic groups containing aromatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6492—Lignin containing materials; Wood resins; Wood tars; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
Abstract
The present invention relates to the polyalcohol containing tannin, preparation method and use.
Description
The present invention relates to the polyalcohol containing tannin (tannin), preparation method and use.
Polyalcohol (especially PPG) yield is big and particularly for preparing polyurethane (PU), such as PU flexible foams
Or PU rigid foams.
Industrially the demand for providing the polyalcohol prepared using natural material is continuously increased.In the context of the present invention
In, term " natural material " refers to the material from regenerative resource, such as trees or other natural growing plants.
US 3,546,199 and US 3,654,194 discloses a kind of sub- by using the carbonic acid as reactant and solvent
The method that ethyl ester prepares lignin and tannin alcoxylates, wherein NaOH or KOH are as catalyst.In being applied in PU,
Using ethylene carbonate and NaOH or KOH as catalyst is used to need necessary post processing.In view of OH values, products obtained therefrom
Viscosity is still of a relatively high.
It is thus known that product and method there are some shortcomings.For example, as it is known that method typically results in product with higher
Viscosity, make them unsuitable for preparing polyurethane.In addition, generally requiring complicated and expensive post-processing step, this also results in discarded
The generation of thing and the poor efficiency for starting material used.
Therefore, it is an object of the invention to overcome disadvantages mentioned above, such as necessary cumbersome post-processing step.Especially
Ground, it is an object of the invention to obtain the product liquid that can be used for preparing polyurethane products.
Another purpose be to provide one kind be at least partially based on sustainable (that is, naturally occurring or reproducible) raw material (with
Raw material based on mineral oil is opposite) polyalcohol.
Unexpectedly, inventor has found products therefrom with being based on polyfunctionality alcohol (such as glycerine or D-sorbite)
Standard multiple alcohol, which is compared, also has higher pentane compatibility.
In addition, the polyalcohol of the present invention can improve the fireproofing function of gained polyurethane.
In particular a kind of method for preparing the polyalcohol P containing tannin of the purpose of the present invention, methods described by 50ppm extremely
By 1 to 30 weight % tannin T, 1 to 30 weight % at least one in the presence of 50000ppm at least one base catalyst C
Degree of functionality is carried out for the epoxyalkane A reactions that 2 to 6 polyalcohol S and at least one each molecule have 2 to 4 carbon atoms,
It is each based on T, S, A and C cumulative weight meter.
Other objects of the present invention include：
The polyalcohol P containing tannin as obtained by the method for the present invention,
The polyalcohol P containing tannin as obtained by the method for the present invention is used for the purposes for preparing polyurethane, and
Viscosity is 500 to the 80000mPas polyalcohol P containing tannin, and it contains 1 to 30 weight % tannin T, 1
The polyalcohol S and at least one each molecule that at least one degree of functionality to 30 weight % is 2 to 6 have 2 to 4 carbon atoms
Epoxyalkane A, is each based on T, S, A and C cumulative weight meter, the polyalcohol P by 50ppm to 50000ppm at least
Component T, S and A are reacted in the presence of a kind of base catalyst C and obtained.
The polyalcohol containing tannin of the present invention can by with least one diisocyanate or polyisocyanates react and
It is advantageously used in and prepares polyurethane.In addition, the present invention the polyalcohol containing tannin and can pass through the inventive method obtain
Polyalcohol can not have to post processing in advance yet and be used for cosmetic applications.
In a preferred embodiment of the inventive method, using 40 to 90 weight %, preferably 50 to 80 weight %'s
Epoxyalkane A, the cumulative weight meter based on T, S, A and C.In another preferred embodiment of the inventive method, polyalcohol P with
Polyalcohol S is different.In another preferred embodiment of the inventive method, the polyalcohol P containing tannin is liquid at 25 DEG C.
In another preferred embodiment of the inventive method, viscosity that the polyalcohol P containing tannin has for 200 to
80000mPas, preferably 200 to 30000mPas.In another preferred embodiment of the inventive method, the tannin T is selected from can
The tannin of hydrolysis and/or the tannin of non-hydrolysable.
In another preferred embodiment of the inventive method, the tannin T is selected from myrobalan (myrobalan) and/or contained
Shy grass (mimosa).
In another preferred embodiment of the inventive method, polyalcohol S be selected from glycerine, D-sorbite, diethylene glycol,
DPG, trimethylolpropane, toluenediamine TMP, TDA, ethylene glycol and the polyalcohol containing EO and/or the polyalcohol containing PO and
Its mixture, preferably glycerine and/or DPG.
In another preferred embodiment of the inventive method, the epoxyalkane A is selected from oxirane and/or epoxy third
Alkane, preferably expoxy propane.
In another preferred embodiment of the inventive method, the catalyst C is alkaline organic or inorganic catalyst, excellent
Select basic organic catalyst.
In another preferred embodiment of the inventive method, the base catalyst C be selected from KOH, CsOH, NaOH and/
Or nitrogenous catalyst, preferably nitrogenous catalyst.
In a preferred embodiment of the inventive method, the base catalyst C is selected from DMEOA and/or imidazoles, excellent
Select imidazoles.
In another preferred embodiment of the inventive method, using 5 to 25 weight % tannin T, based on T, S, A and C
Cumulative weight meter.
In another preferred embodiment of the inventive method, using 4 to 25 weight % polyalcohol S, based on T, S, A and
C cumulative weight meter.
In another preferred embodiment of the inventive method, using 100ppm to 5000ppm catalyst C, based on T,
S, A and C cumulative weight meter.
Embodiment
In sections below, some embodiments given are intended to illustrate some aspects of invention.
Hydroxyl value (DIN=" Deutsche Industrienorm ", i.e. German Industrial mark are determined according to DIN 53240
It is accurate).
Unless otherwise indicated, according to DIN EN ISO 3219, by using rotor CC25DIN, (rotor is straight at 25 DEG C
Footpath：12.5mm；Measure the internal diameter of cylinder：Rheotec RC20 rotation viscometers 13.56mm) are surveyed under 50/1 second in shear rate
Determine the viscosity of polyalcohol.
Pentane compatibility is determined by being gradually added pentane into product.Add accurate 100g samples pentane and mix
Close.If mixture both becomes without muddiness or not two-phase, add more pentanes and mix again.It is two in mixture
In the case of phase, pentane is evaporated at room temperature until obtaining the product of homogeneous transparent.Pass through the weight to mixture and starting group
The weight divided is compared to determine the pentane amount added.In mixture in the case of muddy, sealed sample and at room temperature
Storage is until there is obvious be separated.Then, using with above-mentioned two-phase system identical method.
Comparative example A
Lupranol 3300 is the three-functionality-degree PPG based on glycerine.It mainly contains secondary hydroxyl and OH values
For 400mg KOH/g samples.Pentane compatibility is 35% at room temperature.
Comparative example B
9346 be the PPG based on sucrose.It mainly contains secondary hydroxyl and OH values are 450mg
KOH/g samples (viscosity (25 DEG C):18400mPa*s).Pentane compatibility is 12% at room temperature.
Comparative example C
PPG based on sucrose.It mainly contains secondary hydroxyl and OH values are 417mg KOH/g sample (viscosity (25
℃):30000mPa*s).Pentane compatibility is 13% at room temperature.
Comparative example D
PPG based on sucrose.It mainly contains secondary hydroxyl and OH values are 511mg KOH/g sample (viscosity (25
℃):30000mPa*s).Pentane compatibility is 9% at room temperature.
Comparative example E
PPG based on sucrose.It mainly contains secondary hydroxyl and OH values are 519mg KOH/g sample (viscosity (25
℃):74179mPa*s).Pentane compatibility is 7% at room temperature.
Embodiment 1
The imidazoles of 36.2g glycerine, 36.2g myrobalan and 500ppm is placed in 300mL reactor.Sealing reaction
Device, purged with nitrogen and start agitator.Temperature is increased to 120 DEG C and adds 167.5g PO., will after all PO is added
Mixture stirs 9.5 hours.Then at 100 DEG C, mixture is vacuumized under reduced pressure 40 minutes.Obtain at room temperature (25 DEG C)
It is the final product (221.1g) of liquid down.
Hydroxyl value:527mg KOH/g
Viscosity (25 DEG C):2930mPa*s
Pentane compatibility:10.7%
Embodiment 2
The imidazoles of 36.2g glycerine, 36.2g sensitive plant and 500ppm is placed in 300mL reactor.Sealing is anti-
Device is answered, is purged with nitrogen and starts agitator.Temperature is increased to 120 DEG C and adds 167.5g PO.After all PO is added,
Reactant mixture is continued into stirring 45 minutes 14 hours.Then at 100 DEG C, mixture is vacuumized under reduced pressure 40 minutes.
Obtain at room temperature as the final product (219.0g) of liquid.
Hydroxyl value:515.5mg KOH/g
Viscosity (25 DEG C):5560mPa*s
Pentane compatibility:10.7%
Embodiment 3
The imidazoles of 27.6g glycerine, 27.6g sensitive plant and 500ppm is placed in 300mL reactor.Sealing is anti-
Device is answered, is purged with nitrogen and starts agitator.Temperature is increased to 120 DEG C and adds 184.7g PO.After all PO is added,
Reactant mixture is continued into stirring 12 hours.Then at 100 DEG C, mixture is vacuumized under reduced pressure 40 minutes.Obtain
It is the final product (218.0g) of liquid at room temperature.
Hydroxyl value:399.5mg KOH/g
Viscosity (25 DEG C):1970mPa*s
Pentane compatibility:21.3%
Embodiment 4
The imidazoles of 27.6g glycerine, 27.6g myrobalan and 500ppm is placed in 300mL reactor.Sealing reaction
Device, purged with nitrogen and start agitator.Temperature is increased to 120 DEG C and adds 184.7g PO., will after all PO is added
Reactant mixture continues stirring 12.5 hours.Then at 100 DEG C, mixture is vacuumized under reduced pressure 40 minutes.Obtain
It is the final product (214.0g) of liquid at room temperature.
Hydroxyl value:412.9mg KOH/g
Viscosity (25 DEG C):1400mPa*s
Pentane compatibility:20.0%
Embodiment 5
The imidazoles of 17.2g glycerine, 17.2g sensitive plant and 1000ppm is placed in 300mL reactor.Sealing
Reactor, purged with nitrogen and start agitator.Temperature is increased to 130 DEG C and adds 205.4g PO.All adding PO
Afterwards, reactant mixture is continued into stirring 4 hours.Then at 100 DEG C, mixture is vacuumized under reduced pressure 40 minutes.Obtain
It is the final product (208.0g) of liquid at room temperature.
Hydroxyl value:273.7mg KOH/g
Viscosity (25 DEG C):701mPa*s
Embodiment 6
The imidazoles (50% aqueous solution) of 17.2g glycerine, 17.2g sensitive plant and 1000ppm is placed in 300mL's
In reactor.Reactor is sealed, is purged with nitrogen and starts agitator.Temperature is increased to 130 DEG C and adds 205.4g PO.
After all PO is added, reactant mixture is continued into stirring 4 hours.Then at 100 DEG C, mixture is vacuumized under reduced pressure
40 minutes.Obtain at room temperature as the final product (206.4g) of liquid.
Hydroxyl value:270.6mg KOH/g
Viscosity (25 DEG C):698mPa*s
Pentane compatibility:>100%
Embodiment 7
The imidazoles (50% aqueous solution) of 20.7g glycerine, 20.7g sensitive plant and 1000ppm is placed in 300mL's
In reactor.Reactor is sealed, is purged with nitrogen and starts agitator.Temperature is increased to 130 DEG C and adds 198.5g PO.
After all PO is added, reactant mixture is continued into stirring 4 hours.Then at 100 DEG C, mixture is vacuumized under reduced pressure
40 minutes.Obtain at room temperature as the final product (211.0g) of liquid.
Hydroxyl value:315.8mg KOH/g
Viscosity (25 DEG C):859mPa*s
Pentane compatibility:37.1%
Embodiment 8
The imidazoles (50% aqueous solution) of 27.6g glycerine, 27.6g sensitive plant and 1000ppm is placed in 300mL's
In reactor.Reactor is sealed, is purged with nitrogen and starts agitator.Temperature is increased to 130 DEG C and adds 184.7g PO.
After all PO is added, reactant mixture is continued into stirring 4 hours.Then at 100 DEG C, mixture is vacuumized under reduced pressure
40 minutes.Obtain at room temperature as the final product (219.0g) of liquid.
Hydroxyl value:410.6mg KOH/g
Viscosity (25 DEG C):1940mPa*s
Pentane compatibility:20.0%
Embodiment 9
The imidazoles (50% aqueous solution) of 34.5g glycerine, 34.5g sensitive plant and 1000ppm is placed in 300mL's
In reactor.Reactor is sealed, is purged with nitrogen and starts agitator.Temperature is increased to 130 DEG C and adds 170.9g PO.
After all PO is added, reactant mixture is continued into stirring 4 hours.Then at 100 DEG C, mixture is vacuumized under reduced pressure
40 minutes.Obtain at room temperature as the final product (225.4.0g) of liquid.
Hydroxyl value:519.9mg KOH/g
Viscosity (25 DEG C):4290mPa*s
Pentane compatibility:10.7%
Embodiment 10
The imidazoles (50% aqueous solution) of 17.2g glycerine, 17.2g myrobalan and 1000ppm is placed in the anti-of 300mL
Answer in device.Reactor is sealed, is purged with nitrogen and starts agitator.Temperature is increased to 130 DEG C and adds 205.4g PO.
After all adding PO, reactant mixture is continued into stirring 4 hours.Then at 100 DEG C, mixture is vacuumized 40 under reduced pressure
Minute.Obtain at room temperature as the final product (225.4.0g) of liquid.
Hydroxyl value:271.3mg KOH/g
Viscosity (25 DEG C):602mPa*s
Pentane compatibility:>100%
Embodiment 11
The imidazoles (50% aqueous solution) of 20.7g glycerine, 20.7g myrobalan and 1000ppm is placed in the anti-of 300mL
Answer in device.Reactor is sealed, is purged with nitrogen and starts agitator.Temperature is increased to 130 DEG C and adds 198.5g PO.
After all adding PO, reactant mixture is continued into stirring 4 hours.Then at 100 DEG C, mixture is vacuumized 40 under reduced pressure
Minute.Obtain at room temperature as the final product (215.9g) of liquid.
Hydroxyl value:325.1mg KOH/g
Viscosity (25 DEG C):781mPa*s
Pentane compatibility:35.1%
Embodiment 12
The imidazoles (50% aqueous solution) of 27.6g glycerine, 27.6g myrobalan and 1000ppm is placed in the anti-of 300mL
Answer in device.Reactor is sealed, is purged with nitrogen and starts agitator.Temperature is increased to 130 DEG C and adds 184.7g PO.
After all adding PO, reactant mixture is continued into stirring 4 hours.Then at 100 DEG C, mixture is vacuumized 40 under reduced pressure
Minute.Obtain at room temperature as the final product (224.2g) of liquid.
Hydroxyl value:414.4mg KOH/g
Viscosity (25 DEG C):1390mPa*s
Pentane compatibility:20.0%
Embodiment 13
The imidazoles (50% aqueous solution) of 34.5g glycerine, 34.5g myrobalan and 1000ppm is placed in the anti-of 300mL
Answer in device.Reactor is sealed, is purged with nitrogen and starts agitator.Temperature is increased to 130 DEG C and adds 170.9g PO.
After all adding PO, reactant mixture is continued into stirring 4 hours.Then at 100 DEG C, mixture is vacuumized 40 under reduced pressure
Minute.Obtain at room temperature as the final product (217.2g) of liquid.
Hydroxyl value:507.2mg KOH/g
Viscosity (25 DEG C):2390mPa*s
Pentane compatibility:13.8%
Embodiment 14
By Aethoxy Sklerols (OH value=400) of the 80.2g based on glycerine, 38.6g sensitive plant and 1000ppm imidazoles
(50% aqueous solution) is placed in 300mL reactor.Reactor is sealed, is purged with nitrogen and starts agitator.Temperature is increased
Add to 130 DEG C and add 120.9g PO.After all PO is added, reactant mixture is continued into stirring 4 hours.Then 100
At DEG C, mixture is vacuumized under reduced pressure 40 minutes.Obtain at room temperature as the final product (216.6g) of liquid.
Hydroxyl value:395.3mg KOH/g
Viscosity (25 DEG C):3850mPa*s
Pentane compatibility:20.0%
Embodiment 15
By the 65.8g Aethoxy Sklerol (OH value=400) based on glycerine, 42.1g sensitive plant and 1000ppm imidazoles
(50% aqueous solution) is placed in 300mL reactor.Reactor is sealed, is purged with nitrogen and starts agitator.Temperature is increased
Add to 130 DEG C and add 131.8g PO.After all PO is added, reactant mixture is continued into stirring 5 hours.Then 100
At DEG C, mixture is vacuumized under reduced pressure 40 minutes.Obtain at room temperature as the final product (217.4g) of liquid.
Hydroxyl value:385.6mg KOH/g
Viscosity (25 DEG C):6140mPa*s
Pentane compatibility:19.4%
Embodiment 16
By Aethoxy Sklerol (hydroxyl value=400), 44.8g sensitive plant and 1000ppm imidazoles of the 54.7g based on glycerine
(50% aqueous solution) is placed in 300mL reactor.Reactor is sealed, is purged with nitrogen and starts agitator.Temperature is increased
Add to 130 DEG C and add 140.3g PO.After all PO is added, reactant mixture is continued into stirring 5 hours.Then 100
At DEG C, mixture is vacuumized under reduced pressure 40 minutes.Obtain at room temperature as the final product (216.8g) of liquid.
Hydroxyl value:384.0mg KOH/g
Viscosity (25 DEG C):7910mPa*s
Pentane compatibility:19.4%
Embodiment 17
The imidazoles (50% aqueous solution) of 71.5g DPG, 21.8g sensitive plant and 1000ppm is placed in 300mL
Reactor in.Reactor is sealed, is purged with nitrogen and starts agitator.Temperature is increased to 130 DEG C and adds 146.4g's
PO.After all PO is added, reactant mixture is continued into stirring 5 hours.Then at 100 DEG C, mixture is taken out under reduced pressure
Vacuum 40 minutes.Obtain at room temperature as the final product (212.7g) of liquid.
Hydroxyl value:408.8mg KOH/g
Viscosity (25 DEG C):290mPa*s
Pentane compatibility:43.8%
Embodiment 18
By Aethoxy Sklerol (hydroxyl value=490), 16.1g sensitive plant and 1000ppm miaow of the 116.6g based on D-sorbite
Azoles (50% aqueous solution) is placed in 300mL reactors.Reactor is sealed, is purged with nitrogen and starts agitator.Temperature is increased
Add to 130 DEG C and add 107.0g PO.After all PO is added, reactant mixture is continued into stirring 5 hours.Then 100
At DEG C, mixture is vacuumized under reduced pressure 40 minutes.Obtain at room temperature as the final product (212.4g) of liquid.
Hydroxyl value:381.8mg KOH/g
Viscosity (25 DEG C):7540mPa*s
Pentane compatibility:22.5%
Embodiment 19
By Aethoxy Sklerol (hydroxyl value=400), 47.0g sensitive plant and 1000ppm imidazoles of the 45.8g based on glycerine
(50% aqueous solution) is placed in 300mL reactor.Reactor is sealed, is purged with nitrogen and starts agitator.Temperature is increased
Add to 130 DEG C and add 147.0g PO.After all PO is added, reactant mixture is continued into stirring 5 hours.Then 100
At DEG C, mixture is vacuumized under reduced pressure 40 minutes.Obtain at room temperature as the final product (222.8g) of liquid.
Hydroxyl value:379.3mg KOH/g
Viscosity (25 DEG C):8920mPa*s
Pentane compatibility:19.4%
Sensitive plant=from acacia mearnsii (Black Wattle tree) (the category kind for originating in the Acacia of Australia) tree
The tanning extract of skin
Myrobalan=the tanning extract from myrobalan (Terminalia chebula) tree.
Compared with comparative example C, embodiment 3,4,8,12,14,15,16,17,18 and 19 is shown with suitable OH values
Improved pentane compatibility.The viscosity of these embodiments significantly decreases compared with comparative example C.
Compared with comparative example D and E, embodiment 1,2,9 and 13 shows that improved pentane is compatible with suitable OH values
Property.The viscosity of these embodiments significantly decreases compared with comparative example D and E.
Compared with comparative example B, embodiment 13 shows improved pentane compatibility with suitable OH values.The embodiment
Viscosity significantly decreased compared with comparative example B.
Further, since using preferable catalyst (organic nitrogen-containing basic catalyst), need not post-process after the reaction.
The catalyst can retain in the product.
Claims (38)
1. preparing the method for the polyalcohol P containing tannin, methods described passes through at least one alkalescence in 100ppm to 5000ppm
In the presence of catalyst C by 1 to 30 weight % tannin T, 1 to 30 weight % at least one degree of functionality be 2 to 6 polyalcohol S
There is the epoxyalkane A reactions of 2 to 4 carbon atoms with least one each molecule and carry out, be each based on the tired of T, S, A and C
Gauge is counted weight, wherein the catalyst C is basic organic catalyst, selected from nitrogenous catalyst.
2. polyalcohol P of the preparation containing tannin according to claim 1 method, wherein the ring using 40 to 90 weight %
Oxygen alkane A, the cumulative weight meter based on T, S, A and C.
3. polyalcohol P of the preparation containing tannin according to claim 2 method, wherein the ring using 50 to 80 weight %
Oxygen alkane A, the cumulative weight meter based on T, S, A and C.
4. polyalcohol P of the preparation containing tannin according to claim 1 or 2 method, wherein polyalcohol P and polyalcohol S
It is different.
5. polyalcohol P of the preparation containing tannin according to claim 1 or 2 method, wherein described contain the more of tannin
First alcohol P is liquid at 25 DEG C.
6. polyalcohol P of the preparation containing tannin according to claim 1 or 2 method, wherein described contain the more of tannin
The viscosity that first alcohol P has is 200 to 80000mPas.
7. polyalcohol P of the preparation containing tannin according to claim 6 method, wherein the polyalcohol containing tannin
The viscosity that P has is 200 to 30000mPas.
8. polyalcohol P of the preparation containing tannin according to claim 1 or 2 method, wherein be selected from can water by the tannin T
The tannin of solution and/or the tannin of non-hydrolysable.
9. polyalcohol P of the preparation containing tannin according to claim 1 or 2 method, wherein the tannin T is selected from myrobalan
And/or sensitive plant.
10. polyalcohol P of the preparation containing tannin according to claim 1 or 2 method, wherein the polyalcohol S is selected from
Glycerine, D-sorbite, diethylene glycol, DPG, trimethylolpropane, toluenediamine TMP, TDA, ethylene glycol and containing EO's
Polyalcohol and/or polyalcohol and its mixture containing PO.
11. polyalcohol P of the preparation containing tannin according to claim 10 method, wherein the polyalcohol S is selected from third
Triol and/or DPG.
12. polyalcohol P of the preparation containing tannin according to claim 1 or 2 method, wherein the epoxyalkane A is selected
From oxirane and/or expoxy propane.
13. polyalcohol P of the preparation containing tannin according to claim 12 method, wherein the epoxyalkane A is selected from
Expoxy propane.
14. polyalcohol P of the preparation containing tannin according to claim 1 or 2 method, wherein the catalyst C is selected from
DMEOA and/or imidazoles.
15. polyalcohol P of the preparation containing tannin according to claim 14 method, wherein the catalyst C is selected from miaow
Azoles.
16. polyalcohol P of the preparation containing tannin according to claim 1 or 2 method, wherein using 5 to 25 weight %
Tannin T, the cumulative weight meter based on T, S, A and C.
17. polyalcohol P of the preparation containing tannin according to claim 1 or 2 method, wherein using 4 to 25 weight %
Polyalcohol S, the cumulative weight meter based on T, S, A and C.
18. polyalcohol P of the preparation containing tannin according to claim 1 or 2 method, wherein using 100ppm extremely
5000ppm catalyst C, the cumulative weight meter based on T, S, A and C.
19. the polyalcohol P containing tannin obtained by the method according to any one of claim 1 to 18.
20. the polyalcohol P containing tannin obtained by the method according to any one of claim 1 to 18 is used to prepare
The purposes of polyurethane.
21. the polyalcohol P containing tannin, its viscosity be 500 to 80000mPas, and its contain 1 to 30 weight % tannin T,
The polyalcohol S and at least one each molecule that 1 to 30 weight % at least one degree of functionality is 2 to 6 have 2 to 4 carbon atoms
Epoxyalkane A, be each based on T, S, A and C cumulative weight meter, the polyalcohol P by 100ppm to 5000ppm extremely
Component T, S and A are reacted and obtained in the presence of a kind of few base catalyst C, wherein the base catalyst C is selected from nitrogenous urge
Agent.
22. the polyalcohol P according to claim 21 containing tannin, it contains 40 to 90 weight % epoxyalkane A.
23. the polyalcohol P according to claim 22 containing tannin, it contains 50 to 85 weight % epoxyalkane A.
24. the polyalcohol P containing tannin according to claim 21 or 22, wherein polyalcohol P are different from polyalcohol S.
25. the polyalcohol P containing tannin according to claim 21 or 22, wherein the polyalcohol P containing tannin is at 25 DEG C
For liquid.
26. the polyalcohol P containing tannin according to claim 21 or 22, wherein what the polyalcohol P containing tannin had
Viscosity is 200 to 80000mPas.
27. the polyalcohol P according to claim 26 containing tannin, wherein the viscosity that the polyalcohol P containing tannin has
For 200 to 30000mPas.
28. the polyalcohol P containing tannin according to claim 21 or 22, wherein the tannin T is selected from hydrolyzable list
Peaceful and/or non-hydrolysable tannin.
29. the polyalcohol P containing tannin according to claim 21 or 22, wherein tannin T are selected from myrobalan and/or bashfully
Grass.
30. the polyalcohol P containing tannin according to claim 21 or 22, wherein the polyalcohol S is selected from glycerine, mountain
Pears sugar alcohol, diethylene glycol, DPG, trimethylolpropane, toluenediamine TMP, TDA, ethylene glycol and polyalcohol containing EO and/
Or polyalcohol and its mixture containing PO.
31. the polyalcohol P according to claim 30 containing tannin, wherein the polyalcohol S is selected from glycerine and/or two
Propane diols.
32. oxirane and/or ring are selected from according to the polyalcohol P containing tannin of claim 21 or 22, wherein epoxyalkane A
Ethylene Oxide.
33. according to the polyalcohol P containing tannin of claim 32, wherein epoxyalkane A is selected from expoxy propane.
34. according to the polyalcohol P containing tannin of claim 21 or 22, wherein the base catalyst C be selected from DMEOA and/
Or imidazoles.
35. according to the polyalcohol P containing tannin of claim 34, wherein the base catalyst C is selected from imidazoles.
36. according to the polyalcohol P containing tannin of claim 21 or 22, wherein the polyalcohol containing tannin contains 5 to 25 weights
Measure % tannin T, the cumulative weight meter based on T, S, A and C.
37. according to the polyalcohol P containing tannin of claim 21 or 22, wherein the polyalcohol containing tannin contains 4 to 25 weights
Measure % polyalcohol S, the cumulative weight meter based on T, S, A and C.
38. according to the polyalcohol P containing tannin of claim 21 or 22, wherein the catalyst using 100ppm to 5000ppm
C, the cumulative weight meter based on T, S, A and C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP13172508.7 | 2013-06-18 | ||
| EP13172508 | 2013-06-18 | ||
| PCT/EP2014/060949 WO2014202351A1 (en) | 2013-06-18 | 2014-05-27 | Tannin-containing polyols, their production and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105308088A CN105308088A (en) | 2016-02-03 |
| CN105308088B true CN105308088B (en) | 2018-03-27 |
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|---|---|
| EP (1) | EP3010949B1 (en) |
| JP (1) | JP6518236B2 (en) |
| KR (1) | KR102228966B1 (en) |
| CN (1) | CN105308088B (en) |
| BR (1) | BR112015031873A2 (en) |
| MX (1) | MX362070B (en) |
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| FR3056985B1 (en) * | 2016-10-04 | 2020-06-19 | Arkema France | PROCESS FOR THE MANUFACTURE OF ALCOXYLATED POLYPHENOLS |
| WO2019099398A1 (en) * | 2017-11-14 | 2019-05-23 | Hexion, Inc. | Alkoxylation of lignins |
| CN111116867B (en) * | 2019-12-31 | 2022-08-26 | 南京林业大学 | Tannin extract-based epoxy resin and preparation method thereof |
| CN111217977B (en) * | 2019-12-31 | 2022-02-11 | 南京林业大学 | Tannin extract-based polyurethane rigid foam and preparation method and application thereof |
| CN111945462B (en) * | 2020-07-21 | 2022-07-26 | 华南理工大学 | Lignin/tannin composite polyurethane coating and preparation method thereof |
| CN115612441B (en) * | 2022-12-15 | 2023-05-09 | 山东一诺威聚氨酯股份有限公司 | Environment-friendly antibacterial adhesive for wood boards and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3654194A (en) * | 1967-02-06 | 1972-04-04 | Kaiser Aluminium Chem Corp | Process for producing polyoxyalkylene ether-polyols from lignin and tannin and products so made |
| CN1541235A (en) * | 2001-08-15 | 2004-10-27 | Process to manufacture polyurethane products using polymer polylos in which carrier polyol is tertiary amone based polyol | |
| EP1923417A1 (en) * | 2006-11-13 | 2008-05-21 | Bayer MaterialScience AG | Process for the preparation of polyether-ester polyols |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2011107366A1 (en) * | 2010-03-02 | 2011-09-09 | Basf Se | Method for producing polyurethanes |
| EP2542607A1 (en) * | 2010-03-02 | 2013-01-09 | Basf Se | Method for producing polyurethane hard foam materials |
| US20120232180A1 (en) * | 2011-03-08 | 2012-09-13 | Basf Se | Process for the production of polyurethane rigid foams |
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- 2014-05-27 SG SG11201510364SA patent/SG11201510364SA/en unknown
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- 2014-05-27 MX MX2015017638A patent/MX362070B/en active IP Right Grant
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3654194A (en) * | 1967-02-06 | 1972-04-04 | Kaiser Aluminium Chem Corp | Process for producing polyoxyalkylene ether-polyols from lignin and tannin and products so made |
| CN1541235A (en) * | 2001-08-15 | 2004-10-27 | Process to manufacture polyurethane products using polymer polylos in which carrier polyol is tertiary amone based polyol | |
| EP1923417A1 (en) * | 2006-11-13 | 2008-05-21 | Bayer MaterialScience AG | Process for the preparation of polyether-ester polyols |
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| BR112015031873A2 (en) | 2017-07-25 |
| RU2016101123A (en) | 2017-07-24 |
| JP6518236B2 (en) | 2019-05-22 |
| KR20160021270A (en) | 2016-02-24 |
| EP3010949A1 (en) | 2016-04-27 |
| WO2014202351A1 (en) | 2014-12-24 |
| MX2015017638A (en) | 2016-08-08 |
| SG11201510364SA (en) | 2016-01-28 |
| MX362070B (en) | 2019-01-07 |
| KR102228966B1 (en) | 2021-03-17 |
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